Method for the preparation of
z-amevo-l-alkanols

ABSTRACT

THE REDUCTIVE AMINATION OF 2-KETO-1-ALKANOLS PRODUCES 2-AMINO-1-ALKANOLS. THE PRODUCTS PREPARED IN ACCORDANCE WITH THE INVENTION ARE EMULSIFYING AGENTS THAT FIND APPLICATION IN THE PREPARATION OF FLOOR POLISHES, SHOE POLISHES, AUTOMOBILE CLEANSERS-POLISHES, EMULSION PASTE WAXES, AND SUBSTITUTED PIPERAZINES BY MEANS OF A CYCLIC REDUCTIVE AMINATION REACTION. FURTHER, ALKYLENE OXIDES MAY BE REACTED WITH THE AMINO-ALKANOLS TO YIELD NITROGEN-CONTAINING POLYETHER POLYOLS USEFUL IN THE PREPARATION OF POLYURETHANES.

United States Patent 27,098 METHOD FOR THE PREPARATION OF Z-AMINO-l-ALKANOLS Stanley B. Cavitt and George P. Speranza, Austin, Tex.,

assignors to Jelferson Chemical Company, Inc., Houston, Tex.

N0 Drawing. Original No. 3,448,153, dated June 3, 1969,

Ser. No. 553,726, May 31, 1966. Application for reissue Apr. 6, 1970, Ser. No. 26,179

Int. Cl. C07c 91/02, 95/02, 97/02 U.S. Cl. 260-584 4 Claims Matter enclosed in heavy brackets appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE The reductive amination of Z-keto-l-alkanols produces 2-amino-1-alkanols. The products prepared in accordance with the invention are emulsifying agents that find application in the preparation of floor polishes, shoe polishes, automobile cleansers-polishes, emulsion paste waxes, and substituted piperazines by means of a cyclic reductive amination reaction. Further, alkylene oxides may be reacted with the amino-alkanols to yield nitrogen-containing polyether polyols useful in the preparation of polyurethanes.

This invention is concerned with the preparation of Z-arnino-l-alkanols. More particularly, this invention is concerned with the preparation of Z-amino-l-alkanols by the reductive amination of 2-keto-1-alkanols.

It is well known that l-amino-Z-alkanols may be obtained by the reaction of alkylene oxides with ammonia and primary and secondary amines. However, this reaction is quite specific and always leads to the product having the amino group attached to the number one carbon atom and the hydroxyl group attached to the number two carbon atom. These compounds are the well known isoalkanolamines. Heretofore there has been no convenient method for the preparation of the Z-amino-l-alkanols, which are structural isomers of the isoalkauolamines. We have now discovered that the 2-amino-1-alkanols can be obtained in good yield by the reductive amination of 2- keto-l-alkanols over specific hydrogenation catalysts.

The products prepared in accordance with our invention, and particularly 2-amino-1-propanol, are emulsifying agents that find application in the preparation of floor polishes, shoe polishes, automobile cleaners-polishes and emulsion paste waxes. Further, these compounds may be employed in the preparation of substituted piperazines by means of a cyclic reductive amination reaction. Still further, alkylene oxides, and particularly propylene oxide, may be reacted with the aminoalkanols to yield nitrogencontaining polyether polyols useful in the preparation of polyurethanes.

It has previously been reported by Berlin and Sycheva, J. Gen. Chem. (USSR) 20, 577 (1950); CA. 44, 7765f, that the reductive amination of acetol over platinum black failed to yield the desired Z-amino-l-propanol. They were able to obtain a 20% yield of the product when acetol was treated with aqueous ammonium hydroxide in the presence of Raney nickel and hydrogen.

We have found that when a promoted nickel or cobalt catalyst is employed in the reaction much higher yields can be obtained and amines may be used in place of ammonia to give N-substituted aminoalkanols. The reaction is conducted in the presence of hydrogen at a temperature within the range of from about 50 to 20 C. and preferably within a range of from about 75 to 150 C. using a Re. 27,098 Re'issued Mar. 23, 1971 is reacted in the presence of hydrogen and the hydrogenation catalyst with a compound having the formula R'NH;

to yield a 2-amino-1-alkauol having the formula wherein R and R are selected from the group consisting of hydrogen and aliphatic and aromatic hydrocarbon radicals containing from 1 to about 20 carbon atoms. Thus, suitable amino compounds for use in our process include ammonia, methylamine, ethylamine, cyclohexylamine, isopropylamine, dodecylamiue, octadecylamine, aniline, benzylamine, p-nonylaniline, 2-phenylethylamiue and 2- phenylpropylamine. Suitable 2-keto-l-alkanols include those in which R is hydrogen, methyl, ethyl, octadecyl, cyclohexyl, phenyl, benzyl and nonylphenyl. The preferred starting materials are ammonia and acetol.

Promoted catalysts are well known in the hydrogenation art. The particular catalysts for use in our process comprise a metal selected from the class consisting of nickel and cobalt promoted with one or more metals from Groups I-B and VI-B of the 'Periodic Table. Examples of acceptable promoting metals include copper, chromium, molybdenum, tungsten and mixtures thereof. Preferred promoters are mixtures of copper and chromium. A typical catalyst will comprise from about 60 to mol percent nickel or cobalt and 40 to 15 mol percent promoters such as, for example, 14 to 37 mol percent copper and l to 5 mol percent chromium. The metals may be employed in the form of their oxides or in the form of the free metals. Chromium is preferably present as a nonreducible oxide.

Our process will be further illustrated by the following iexamples' EXAMPLE I To a 1,000 ml. stirred autoclave were charged a solution of 111 grams (1.5 mols) of acetol in 111 ml. of water and 50 grams of a nickel-copper-chrorma catalyst. The reactor was flushed with hydrogen and charged with 102 grams (6.0 mols) of anhydrous ammonia. Hydrogen, was added to a pressure of 500 p.s.i.g. and the reactor was then heated to approximately 150 C. for one hour. The reaction mixture was cooled, filtered to remove catalyst and subjected to aspirator vacuum for 30 to 45 minutes to remove the excess ammonia. More water and ammonla were removed from the product by distillation at atmospheric pressure and the product was then recovered by vacuum fractionation. There was obtained 58 grams of Z-amino-l-propanol having a boiling point of 77-430 C. at 15 mm. pressure and an index of refraction of 1.4482. An additional 23 grams of impure amine was obtained.

EXAMPLE II To the 1,000 m1. stirred autoclave were added 50 grams of a nickel-copper-chromia catalyst and a solution of 222 grams (3.0 mols) of acetol in ml. of methanol. The

reactor was flushed with hydrogen and .240 grams (12.0 mols) of anhydrous ammonia was added. The reactor was then pressured to 500 pounds with hydrogen heated to 100 C. and repressured to 3,000 p.s.i.g. with hydrogen as necessary. The reaction required approximately one hour for completion. After heating for an additional 30 minutes the reaction mixture was cooled, rinsed out with 50 ml. of methanol, filtered and stripped on a steam bath under aspirator vacuum. Distillation at 15 1mm. gave 100 grams of 2-amino-1-propanol and 74 grams of residue.

EXAMPLE III Example I was repeated except that 50 grams of a cobalt-copper-chromia catalyst was employed. The reaction stopped after approximately one-half hour. A yield of 34 grams of 2-amino-l-propanol was obtained.

EXAMPLE IV To the 1,000 ml. stirred autoclave were added 50 grams of a nickel-copper-chromia catalyst and a solution consisting of 111 grams (1.5 mols) of acetol in 55 grams of ethanol, followed by the addition of 354 grams (6.0 mols) of isopropylamine, with stirring. The reactor was flushed with hydrogen, pressured to 1,000 p.s.i.g. with hydrogen and heated to 100 C. The reactor was repressured to 3,000 p.s.i.g. with hydrogen, as necessary. The reaction was allowed to proceed at approximately 100 C. for four hours. The product mixture was then rinsed from the reactor with 50 ml. of methanol, filtered, stripped to 50 C. on a steam bath under aspirator vacuum and distilled to give 112 grams of 2-(isopropylamino)-1-propanol having a boiling point of 65-66 C. at 15 mm. pressure.

EXAMPLE V Example IV was repeated using 111 grams of water instead of the 55 grams of ethanol. A yield of 58 grams of 2-(isopropylamino)-1-propanol and 17 grams of an unidentified product having a boiling point of 7577 C. at 15 mm. pressure was obtained. The unidentified product was believed to be 2,2-isopropyliminobis(l-propanol) resulting from the further reaction of acetol with 2- (isopropylamino -1-propano1.

Having thus described our invention we claim:

1. A method for the preparation of a Z-amino-lalkanol having the formula which comprises treating a 2-keto-1-alkanol having the formula with a compound having the formula R'NH in the presence of hydrogen and a hydrogenation catalyst comprising nickel or cobalt promoted with at least one metal from Groups LB and VIB at a temperature of from about 200 C., wherein R and R are alkyl, cyclohexyl, phenyl, phenyl-alkyl [or] alkyl-phenyl having up to 20 carbon atoms [.1 or hydrogen.

2. A method as in claim 1 wherein the catalyst is promoted with copper and chromium.

3. A method as in claim 2 wherein the temperature is -150 C.

4. A method as in claim 2 wherein both R and R are hydrogen.

References Cited The following references, cited by the Examiner, are of record in the patented file of this patent or the original patent.

UNITED STATES PATENTS 1,966,478 7/1934 Baur 260585CUX 1,989,325 l/1935 Lommel et al. 260585(C)X 2,618,658 1l/1952 Caldwell 260-584 CHARLES B. PARKER, Primary Examiner R. L. RAYMOND, Assistant Examiner U.S. Cl. X.R. 

